1. Field:
The invention herein relates to alkaline-resistant glasses. While it pertains to glass bodies generally, it has particular pertinence to glasses which are fiberizable.
2. State of the art:
Glass compositions which are exposed for prolonged periods of time benefit from being alkaline (or alkali) resistant. Such glass compositions are also advantageously easily fiberizable. In one particularly useful embodiment, such glass compositions--in the form of fibers--are used in concrete or other cementatious matrixes to provide strength and other properties to the matrix. It would be advantageous to provide such glass compositions at reduced cost, and/or with improved alkali resistance, and/or with enhanced fiberizability.
Alkaline resistance is provided in some glasses by the inclusion of substantial quantities of zirconia and/or titania, such as in AR glasses of Pilkington. Although these materials enhance the alkaline resistance of glass bodies, these are refractory materials which increase the melting point of such glasses. Also, zirconia and titania tend to add cost to the glass inasmuch as these are much more expensive materials than silica, soda, calcia and the usual components of soda lime silica glasses. In addition, it would be advantageous to provide glass compositions having suitable meltability and fiberizability within a wide working range of temperatures.
The lanthanide series metals, often called the rare earth metals, are those metals designated in La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
Lanthanide series metal oxides has been disclosed as a replacement for the calcia component in the starting zirconia-containing composition (Pilkington's Cem-Fil fibers) to improve chemical stability, and glasses from the silica/alumina/yttria/lanthana/titania system show improved resistance to alkali attack when compared with recognized zirconia compositions. See: Molycorp, Inc. brochure entitled: "LN'S...KEY TO TOUGHER CONCRETE, Alkali-resistant glass fibers containing lanthanides", Lanthology 510, B.T.K. July /84. Others have suggested the inclusion of lanthanides in glass compositions for one or more purposes. See: U.S. Pat. Nos. 2,805,166; 3,573,078; 3,783,092; 3,861,925; 4,298,388; 4,330,628; 4,345,037; and 4,521,524; U.K. Patents Nos.1,200,732; 1,243,972; and 1,307,357; U.S.S.R. Patent Document No.988,782; and Japanese Patent Documents Nos.58-64,243; and 58-167,444. Still, further improvements in alkali resistance and/or fiberizability would be advantageous.
The natural mineral zeolites are a group of hydrous alkali and/or alkaline earth aluminosilicates which have an open three-dimensional crystalline framework. While a large number of individual mineral zeolites are known and have been described in the literature, eleven (11) minerals make up the major group of mineral zeolites; analcime, chabazite, clinoptilolite, erionite, ferrierite, heulandite, laumontite, mordenite, natrolite, phillipsite and wairakite. The chemical and physical properties of these major mineral zeolites, as well as the properties of many of the minor mineral zeolites, are described extensively in Lefond (ed.), Industrial Minerals and Rocks (4th Ed., 1975, pp. 1235-1274; Breck, Zeolite Molecular Sieves (1974), especially Chapter 3: and Mumpton (ed.), Mineralogy and Geology of Natural Zeolites, Vol. 4 (Mineralogical Society of America November, 1977). These publications also describe the geologic occurrence of the natural mineral zeolites and some industrial and agricultural uses which have been proposed or in which the natural mineral zeolites are now being used commercially.
It is important to note that the natural mineral zeolites are an entirely different class of materials from the "synthetic zeolites" which have been widely described in many recent articles and patents. Because there is no universally recognized system for naming the synthetic zeolites, and because some of the synthetic materials exhibit x-ray diffraction patterns which suggest possible similarities in structure with the natural mineral zeolites, some reports in the literature and patents have described certain synthetic zeolites as "synthetic" versions of the natural mineral zeolites. Thus, for instance, certain synthetic zeolites have been described as "synthetic analcime" or "synthetic mordenite" and so forth. As noted in the aforementioned Breck reference, however, this approach is technically unsound and has merely led to confusion between the two (2) otherwise distinct classes of materials the natural mineral zeolites and synthetic zeolites. While it has been recognized that there are structural similarities between the two groups, it is clear that the natural mineral zeolites constitute a class of materials significantly separate and distinct in structure and properties from the synthetic zeolites.
Glasses are vitreous materials composed largely of silica. Because silica is a highly refractory material, however, substantial quantities of soda ash, lime or other fluxing materials are added to the silica to permit the glass-forming composition to be melted at reasonable temperatures. Small quantities of other materials, usually elemental materials or oxides, are commonly added to glass melts to provide particular properties such as color or chemical resistance to the finished glass. One experiment has been reported in which a clinoptilolite and glass mixture was fired at 800.degree. C. (well below the melting point of either) to produce what was described as a porous low density glass composition; see Mumpton, supra, p. 197, referring to Tamura Japanese published application 74/098,817 (1974). Also, see "Safety evaluation of simulated high-level waste glass products, (1). Thermal stability." Banba, Taunetaka; Tashiro, Shingo (Tokal Res. Establ. Japan at Energy Res. Inst., Tokal, Japan). Report 1980, JAERI-M-8706, 20 pp. (Japan).